Water-insoluble azo-dyestuff and fiber dyed therewith



Patented Get. 31, 1933 as fs rrrs rArsN OFFIQE WATEllt-IN SOLUBLE AZO-DYESTI IFF AND- IFZEER DYED THERE-WITH I Franz Henle andilierbert Kracker, Frankfort-onv the-lViain-I-lochst, Germany, assignors to General Aniline Werks, Inc., New York, N. Y., a corpcration of Delaware No Drawing. Application February '6, 1932, Serial No. 591,444, and in Germany May 9,

10 Claims. (Cl. 260+76) The present invention relates to new water- I insoluble azo-d'estufis and material dyed to fiber.

This application is a continuation-impart application to our U. S. Patent 1,923,202.

We have found that new valuable water-in: soluble aZo-dyestuffs' are obtainable by combining with a diazotized amine of the benzene-, naphthaleneor anthracene series an aroylene-bis- I acetic-acid-arylide of the following general for-.

wherein R and R stand for radicals of the henzene-, naphthaleneor diphenylseries,=the arylide and amine, however, being free from groups which would make the dyestuffs soluble in water,

such as thesulfonic acid or carboxylic acid group. The dyestuffs, thus obtained, yield yellow to red tints and for the greater part have a ver good fastness to light. The hitherto unknown aroylene-bis-aceticacid-arylides-of the following formula:

wherein the term aroylene means the radical -COR-CO- of anaromatic dicarboxylic acid, may be obtained, for instance, by condensing the aroylene bis-acetic acid esters (obtainable by condensation of aromatic dicarboxylic acidchlorides with aceto-acetic acid esters, accordingto the statements in Journal fiir praktische Chemie vol. 74, pages 124-126, and subsequent acid cleavage) with aromatic amines, for. instance, according to the statements in Annal-- en der Chemie, vol. 245, page 3'72, relating to the preparation of benzoyl-acetie acid anilide.

' Furthermore, we have found that the said arylides have such an afiihityi for cotton fiber that,

according to the process hereafter described, dyeings are obtained which, as regards intensity and beauty of shade, surpass the dyeings obtained with] the corresponding aceto ace'tic-acid-mono-aryl ides.

The aroylenebis-acetic-acid arylides have such a high affinity for the vegetable fiber that an intermediate drying of the grounded goods is soluble in water. i

The said arylides, therefore, are useful for developing the dyestufi on the cotton fiber. A large number of the dyeings obtained by developing the said arylides with any diazotized base have a very good fastness to light, Besidesthe dyestuffs have a very good fastness to water, chlorine and boiling with soap and sodium carbonate. They are, therefore, of great value for industrial dyeing purposes.

the usual manner by dyeing or printing or'they can be made in substance or on any of the usual substrata adapted for the production of lakes.

The 'dyestuffsobtained' by this invention are characterized by the following probable general formula:

wherein R and R stand for radicals of the benzene-, naphthaleneor diphenyl-series, R stands R,j fora radical of the benzene-, naphthaleneor anthracene-series, the radicals, however, being free from groups which would make the dyestuffs The following examples serve to illustrate the invention, but they are not'intended' to limit it theretoz I .(a) Grounding liquor (b) Dzaeo solution 1.52 grams of 1-amino-2-methyl-4-nitrobenzene are diazotized in known manner with 2.8 cc.

The dyestuffs can be produced on the fiber in of hydrochloric acid of 22 Be. and 0.72 gram of sodium nitrite dissolved in water. The clear diaZo-solution is rendered neutral to Congo paper by means of about 2 grams of crystallized sodium acetate and the whole is made up to 1 liter.

(0) Dyeing prescription 50 grams of well-boiled cotton yarn are dried and treated for half-an-hour at 30 C. to 40 C. with the grounding liquor, well squeezed or hydroextracted and then developed for half-an-hour in the diazo-solution. The material is then well rinsed, soaped at boiling temperature, rinsed again and dried.

There is obtained a vivid greenish yellow of a very good fastness to light. It also shows a very good fastness to boiling lye, for example, when 50 grams of the dyed material areboiled for 6 hours with 5 cc. of caustic soda solution of 40 B. in 500 cc. of water.

(1)) Diazo printing color 142 grams of 1-amino-2-methyl-5-chlorobenzene are diazotized with 26 cc. of hydrochloric acid of 22 B. and 7.2 grams of sodium nitrite dissolved in water, with addition of ice. The whole is made up to 500 cc. and thickened with 4'70 grams of tragacanth (:1000) and then rendered neutral to Congo paper by means of 30 grams of crystallized sodium acetate.

(0) Printing prescription The cotton fabric is padded with the grounding liquor, dried and then printed with the diazoprinting color. The material is then washed and soaped at boiling temperature.

There is obtained a vivid greenish yellow of very good fastness to chlorine, to boiling lye as defined in Example 1 and tolight.

The dyestuif has the following probable formula:

The dyestuffs has the following probable for mula:

40.4 grams of terephthaloyl-bis-acetic-acidparat'oluidide are dissolved in 100 ccyof hot 2 CH3 Hac- Noz N02 (a) Grounding liquor 20 grams of terephthaloyl-bis-acetic-acid-4- chloro-Z-rnethyl-l-anilide are dissolved in 50 cc. of alcohol, 11 cc. of caustic soda solution of 34 Be. and 35 cc. of water and the solution is poured into 20 00. of Monopol Brilliant Oil, 40 cc. of caustic soda solution of 34 Be. and 900 cc. of water; to the clear solution 25 grams of sodium chloride are added.

N-caustic soda solution and water. Into this solution there is run a diazo solution prepared as follows: 33.6 grams of l-amino-a-methoxy-iznitrobenzene are diazotized in the usual manner with 52 cc. of hydrochloricacid of 22 Be. and 14.4 grams of sodium nitrite, with addition of ice. The diazo-solution is rendered neutral to Congo paper by means of sodium acetate.

After stirring for some hours, the formation of the clyestuif is finished; it is filtered by suction andforms an orange paste of a very good fastness to light. The dyestuff has the following probable formula: I

By using as coupling components any other r aroylene-bis-acetic-acid arylides and as dia zotizf f Coupling component I Tint ing components any other amine, dyestuffs are i I obilalna'ble Whlch ale pafrtly dlstlrb (23) 1-amino-5-ch1oro- Tere hthaIOyLbis-ace- (:reenish yelgulshed by a very g 1331311955 to llght- 2inethylbenzene. tic-acid-1-amido-4-- low. Y

The following table indicates a number of dye- I 1 g g g 2 Y- I S obtainable according 1;, the pre p (24) 2.5-dichlorani1ine. Terephthaloyl-bis ace- Greenish yeless but does not comprise all possibilities for the p eg gg g; preparation of dyestuffs of very good fastness to benzene,

' (25) a aminoanthra- Terephthaloyl-bis-ace- Yellowish '85 ll ght by using other coupling components and quinom timaci Orange other amines, WhlCh components, however, must chloro 2 methox benzene. be free from Qoups w p would rende? the y (26) l-amino-S-chloro- 'lerephthaloyl -bis -ace- Greenish yelstuffs soluble in water; it, therefore, 1s not: in V nm h l nz ti id-l id -g 1 tended to limit the invention to the dyestuffs i g g 1 11161113101186. therein: (27) 2.5-dichl0raniline. Terephthaloyl-bis-ace- Greenish yeltic-acid-l-amido-4- low. chlofio iBl-methoxy- 5 Diazotizin com omet y enzene.

neri t p Couphng component Tmt (28) a aminoanthra- Terephthaloyl bis ace- Y ell o w i s h quinone. tic acid 1 amido 4 orange. metiyl 2.5 dimeth- 1 oxyenzene. F 4 ;i g igfiffii gfifiififigf QS Qf (29) a aminoanthra- Terephthaloyl bi s ace- Y ello Wis h 90 zene. v 1 quinone. t1c-ac1d-1-am1do-4- orange. (2) l-aniinol-meth- Terephthaloyl-bis-acetic- Covered redchlormz'methoxy'is" yl 2 nitrobenacid-ortho-chloranilide. dish yellow. hylben zene. I Z8118. (3) a-amino-anthra- Terephthaloyl-bis-acetic- O o v e re d quinone. acid-para-anisidide. orange. (4) 2.5 dich1orani1ine Terephthaloyl-bis-aeetic- Reddish yel- We claim.

- aoid-a-naphthylamide. 'low. I (5) l-amin(l))-4-ohloro-2- Tereghghalofififle-aeegio- Very reddish 1. The water-insoluble azo-dyestufi's of the nitro enzene. aci nap yami e. y w. e) 2.5-dich1orani1ine" Terephthaloyl-bis-acetic- Brownish yelfongwmg prooa'ble general formulaacid-Z.5-dichlor-anilide. w. (7) 1-a1nino-4-methy1- Isophthaloyl-bis-aoetic- Vivid greenish 2nitrobenzene. 3Cld-al1llld. yellow. G 0 0 (8) 1-amino-2-methy1- Isophthaloyl-bis-acetic- Turbid yellow V l I 4-nitrobenzene. acid-ortho-chlorani1ide. N N (9) a-arnin0-anth1a- Biphenyl-4.4-dicarbonyl- Very reddish I] H quinone. his-acetic-acid-anilide. yellow. N f N (10) l-amino-4 meth- B1phenyl-4.4-dicarbonyl- Orange.

oxy-2-nitroben-' bis-acetio-acid-orthoin zene. chloranilide. w i (ll) l-alminoig mleth- Naphtthoyleiie 1.15dhis Vivig medium 7 y -5 c oro enace ic-aci -anii e. ye ow. I r zene. h] N hth 1 15 b R dd h I wherein R and R stand for radicals of the ben- 12 l-aminoiec oroop oyeneise is yen H 2-nitrobenzene. acetic-acid-ortho-ohlorlow. f gg fi or dlphenyl series, R

anilide, stands for a radical of the benzene-, naphthalene- (13) l -an1ino-4 nitro- Nitroterephthaloyl -his- Reddish yel- 2 methoxybem acetiwcidmtho t01ui low or anthracene se11es, the radicals be1ng i1 ee from zene. dide. sulfomcor carboxylic acid groups, dyeing yellow (14) 2.5-dichloro aniline Nitroterephthaloyl-bis- Greenish yeli low to red shades and being dlstinguished by the r id e. good fastnessv properties, particularly by their '%Z%ttit?f2' zltrztrrslse r good .fasmess to light.

y y chlom z methoxy ben 2. The Water-insoluble azo-dyestufis of the zene. I 1 i i i (16) a-amino-anthra- Chloro-terephthaloyl-bis- Orange. f0 10W ng probable genelall formula" quinone. acetio-aeid-1-amido-4- ejhloro-25-dimethoxyenzene. I (17) 1-a1nino-5-chloro- Terephthaloyl-bis-acetic- Medium yel- R' NHCO (IJH CO R CO ?HCO -NH RI 2-methylbenzene. acid -1-an1ido -4-ch1orolow. N N

2.5-dimethoxybenzene. I H (18) 2.5 -dich1oro-ani- Terephthaloylbis ace- Medium yel- 5- N line. tic acid 1 amide 4 low.

chloro-2.5-dirnethoxyk A, benzene. (19) a aminoanthra Terephthaloyl bis ace- Orange.

quinone. tilelacid2- 1 Iiamidfi 4 e c oro- .5- imet ox benzene, y wherein R and R stand for radicals of the benig egg l l g f e g gga zene series and R" stands for a radical of the ch10", 2 methoxy benzene-, naphthaleneor anthracene-series, the

benzene. Y (21) 2.5-dichloreniline. Terephthaloyl-bis -ace- Greenish yelraiilcals belng r froln Sulfonlc or carboxyhc tic acid 1 amide 5 ac1d groups, dyeing yellow to red shades and being" ggigg 2 methoxy distinguished by their good fastness properties, 35 (22) a aminoanthra Terepht oyl bis ace- Y ell o w i s h partlculalrly y their good faStneSS t light. v

quinone. tic-aci -1 -,amido-5- orange.

0mm 2 methoxy 3. The water insoluble azo dyestufi of the fol b nz n lowlng probable formula:

0on3 a 1 (ll-ONH-C o-en .o 0-C0 (|JHCONH o1 N N 0113 u n cna N I| I Cl Ol dyeing a greenish-yellow shade and being dis- 6. Fiber dyed with the dyestuffs as claimed intinguished by its good fastness properties, parclaim 1. ticularly by its good fastness to light.

i. The water-insoluble azo-dyestuif of the folclaim 2.

lowing probable formula:

i CH3 dyeing a yellowish orange shade and being (115- 8. Fiber dyed with the dyestuff as claimed in tinguished by its good iastness properties, parclaim 3,

ticularly by its good fastness to light.

5. The Water-insoluble azo-dyestuff of the folc1aim 4.

lowing probable formula:

/ N N 0 CH3 0 CH3 III N 20m HnC dyeing a medium yellow shade and being distin- 10. Fiber dyed with the dyestufi as claimed in guished by its good fastness properties, particuclaim 5. larly by its good fastness to light,

'1; Fiber dyed with the dyestuffs as claimed in 9. Fiber dyed with the dyestuff as claimed in FRANZ HENLE. HERBERT KRACKER. 

